CN104805290A - Method for recovering acetic acid, cobalt and manganese from discharged residues of PTA (purified terephthalic acid) film evaporator - Google Patents
Method for recovering acetic acid, cobalt and manganese from discharged residues of PTA (purified terephthalic acid) film evaporator Download PDFInfo
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- CN104805290A CN104805290A CN201510142807.3A CN201510142807A CN104805290A CN 104805290 A CN104805290 A CN 104805290A CN 201510142807 A CN201510142807 A CN 201510142807A CN 104805290 A CN104805290 A CN 104805290A
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Abstract
The invention relates to a method for recovering acetic acid, cobalt and manganese from discharged residues of a PTA (purified terephthalic acid) film evaporator. The method comprises steps as follows: the discharged residues of the film evaporator are beaten with a small amount of water and resin effluent to obtain slurry, the slurry is subjected to solid-liquid separation, filtrate is subjected to sodium type cation exchange resin removal, the most of resin effluent is cooled and returned for beating the discharged residues of the film evaporator, and acetic acid is recovered from a small part of resin effluent with an extraction method or an evaporation method; saturated resin is desorbed by a desorbent, a precipitant is added to a desorbed solution so as to form cobalt and manganese precipitation, the cobalt and manganese precipitation is filtered, and a filter cake is sufficiently washed by water to obtain a cobalt and manganese mixture. The method has the advantages as follows: firstly, the concentration of acetic acid in a residual liquid is increased by reducing residual liquid extraction and increasing circulation, so that the economy of the acetic acid recovering method is improved; secondly, the acetic acid is recovered with the extraction method, thus, the energy is saved, and the recovery rate is increased; thirdly, more than 90% of the desorbent can be recycled, all that is required is to supplement a small quantity of desorbent lost during operation, and accordingly, the economy is greatly improved.
Description
Technical field
The present invention relates to a kind of method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue, this thin-film evaporator blanking residue comes from the thin-film evaporator of oxidation mother liquor impurity removing unit in Production of Terephthalic Acid process.
Background technology
Pure terephthalic acid's (Purified Terephthalic Acid is called for short PTA) is the main raw material producing trevira and resin, mainly adopts p-Xylol (p-Xylene is called for short PX) air oxidation process to produce at present.In PTA production process, for controlling quality product, extraction section oxidation mother liquor is needed to remove different kinds of bonding units process to remove the impurity in this partial mother liquid, this extraction mother liquor is after gas stripping column concentrate, thin-film evaporator evaporation, final with outside the form discharge system of thin-film evaporator blanking residue, thus form PTA thin-film evaporator blanking residue.PTA thin-film evaporator blanking residue accounts for 0.5 ~ 0.9wt% of PTA output.If national PTA production capacity was by 3,500 ten thousand tons in 2014, PTA thin-film evaporator blanking residue will reach 18 ~ 320,000 tons.
PTA thin-film evaporator blanking residue temperature is 150 ~ 220 DEG C, main component is the wet part such as acetic acid, water, phenylformic acid, p-methylbenzoic acid, terephthalic acid, m-phthalic acid, phthalic acid, p-carboxybenzaldehyde, to aromatic carboxylic acid such as carboxyl phenylcarbinol, Fluorenone dicarboxylic acid, and cobalt manganese bromine plasma, wherein contain acetic acid 5 ~ 20wt%, containing cobalt and manganese totally 0.7 ~ 1.5wt%.In industrial production general water (de-mineralized water or service water) to PTA thin-film evaporator blanking residua beating and cooling to form residue slurry, this residue slurry is called PTA oxidation residua.Usually, this residue slurry can be filtered, then recovery of benzoic acid etc. from filter cake, Call Provision manganese etc. from filtrate.
Acetic acid containing about 1 ~ 5wt% in filtrate (hereinafter referred to as raffinate) after residue slurry filtration, because concentration is too low, usual method is that waste water is removed in discharge.Chinese patent ZL200810229404.2, ZL97103884.8, ZL97119183.2 mention the method recovery of acetic acid with evaporative condenser, and the Acetic Acid-Water solution of recovery then returns in PTA device, but this is only applicable to the higher situation of acetate concentration.For residue slurry filtrate, if adopt the method for evaporation, then because residue slurry filtrate evaporative process needs to consume steam, and after the dilute acetic acid that evaporation obtains returns dehydration tower, Acetic Acid-Water is separated also needs to consume steam, these two strands of steam consumptions are compared with the value of gained acetic acid, when acetate concentration in residue slurry filtrate reaches more than 6wt%, method of evaporation recovery of acetic acid just has an economic benefit, and in residual night, acetate concentration only has about 1 ~ 5wt% usually.
About the recovery of cobalt manganese in the filtrate of residue slurry, openly report in document that maximum is base exchange method, namely the metal ions such as the cobalt manganese in cationic exchange resin adsorption filtrate are used, resolve with resolving agent again after resin is saturated, as Chinese patent application 87107709.4 cationic exchange resin adsorption, sodium-acetate-acetic acid is resolved, Chinese patent ZL93107509.2 strong-acid cation-exchange resin adsorbs, inorganic acid or organic acid are resolved, Chinese patent ZL98113765.2 sodium form strong-acid cation-exchange resin, sodium-acetate-acetic acid is resolved, desorbed solution evaporation concentration obtains Cobaltous diacetate/manganese acetate, Chinese patent ZL99121153.7 hydrogen type strong acid Zeo-karb, strong acid is resolved, desorbed solution adds Na
2cO
3precipitate to obtain cobaltous carbonate/manganous carbonate, Chinese patent application 200410030379.7 ammonium type strong resin absorption, ammonium acetate are resolved, desorbed solution evaporation concentration obtains Cobaltous diacetate/manganese acetate, Chinese patent application 200810091455.3 ammonium type cationic exchange resin adsorption, ammonium acetate are resolved, ammonium bicarbonate precipitation obtains cobaltous carbonate/manganous carbonate, Chinese patent ZL200710020477.6 Na
2sO
4parsing, P204 Extraction of Cobalt manganese, sulphuric acid soln are stripped, condensing crystal obtains rose vitriol/manganous sulfate, Chinese patent application 200910169484.1 hydrogen type strong acid positive resin absorption, inorganic acid are resolved, adjust pH value except Fe and Cr, extraction removes Zn, last electrolytic process obtains cobalt manganese, and inorganic acid is resolved agent and generally selected hydrochloric acid, sulfuric acid, Hydrogen bromide etc.Resolve agent in these methods can not recycle, parsing agent consumption is larger.
Summary of the invention
In order to overcome the above-mentioned defect under prior art, the object of the present invention is to provide a kind of method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue, even if the recovery that the method carries out acetic acid and cobalt manganese for the raffinate of acetic acid low concentration also has higher economic benefit, can more than 65% be reached to the rate of recovery of acetic acid in PTA thin-film evaporator blanking residue.
Technical scheme of the present invention is:
From PTA thin-film evaporator blanking residue, a method for recovery of acetic acid and cobalt manganese, comprises the steps:
(1) pull an oar: with water to PTA thin-film evaporator blanking residua beating, form residue slurry;
(2) solid-liquid separation: solid-liquid separation is carried out to described residue slurry, obtains raffinate;
(3) cationic exchange: described raffinate is removed sodium form Zeo-karb, the cobalt manganese in raffinate is attracted on resin, and the rest part of raffinate flows through resin and obtains resin flow fluid;
(4) Call Provision manganese: desorbed solution is resolved to obtain in the saturated rear parsing agent of Zeo-karb, precipitation agent is added to form cobalt manganese precipitation in desorbed solution, filtration obtains coarse filtration cake and filtrate, fully wash coarse filtration cake with washing water again and obtain filter cake and wash filtrate, filter cake is the violent precipitation mixture of cobalt, return PTA oxidation unit after being pulled an oar by filter cake acetic acid to use, filtrate is the aqueous solution of resolving agent containing high density, this filtrate returned and recycle as Zeo-karb parsing agent, wash filtrate removes waste water;
(5) resin flow fluid shunting also recovery of acetic acid: the major part of described resin flow fluid is returned described step (1) as circulation fluid and jointly participates in pulling an oar with water; Remaining part presses operational path A or operational path B with recovery of acetic acid as Extract;
Operational path A:
(6) extract: add extraction agent to described Extract and extract;
(7) decant: carry out decant to extraction liquid, obtains oil phase and aqueous phase, and described oil phase is the extraction agent phase being rich in acetic acid; Containing a small amount of extraction agent in described aqueous phase;
(8) be separated: described oil phase is sent to PTA device dehydration tower to reclaim extraction agent and acetic acid, wherein extraction agent returns described step (6) recycle; Described aqueous phase is sent to PTA device entrainer recovery tower and at the bottom of tower, discharge waste water to reclaim extraction agent simultaneously;
Operational path B:
(9) flash distillation: to the flash distillation again of the first heating evaporation of described Extract, flash distillation gas phase is Acetic Acid-Water steam, and flash distillation liquid phase is waste water;
(10) dewater: flash distillation gas phase goes PTA device dehydration tower with recovery of acetic acid.
Described parsing agent is preferably the aqueous solution of the mixture of one or more in sodium-chlor, Sodium Bromide, Sodium Fluoride, sodium iodide, SODIUMNITRATE, sodium sulfate, in this aqueous solution, the mass concentration of solute is preferably 2 ~ 15wt%, resolve agent to recycle on stream, extraneous only need supplement operating to lose on a small quantity, magnitude of recruitment is that resin single resolves 2 ~ 12% of parsing agent total amount used.
Described precipitation agent is preferably the mixture of one or more in sodium sulphite, sodium phosphate, sodium iodate, sodium carbonate, sodium formiate, sodium oxalate.
Described washing water are preferably de-mineralized water, the dehydration tower draining of PTA device or PTA refined wastewater, and consumption can be 5 ~ 25 times of washing filter cake quality to be washed, and temperature is preferably 30 ~ 50 DEG C.
Described extraction agent is preferably the mixture of one or more in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate.
Extraction temperature is preferably 40 ~ 60 DEG C, and the mass ratio of extraction agent and Extract is preferably 1.5 ~ 4:1.
The outlet of preferred control heating evaporation is 100 ~ 120 DEG C, normal pressure, and vaporization rate is 60 ~ 90%, and should control flashing pressure is normal pressure, makes to reach more than 8wt% containing acetic acid in flash distillation gas phase.
For the aforementioned method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue described in any one, preferably make described circulation fluid return step (1) again after cooling, preferably make described circulation fluid temperature after cooling be down to 20 ~ 40 DEG C.
For the aforementioned method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue described in any one, preferably make the described resin flow fluid of 60 ~ 95% as described circulation fluid.
For the aforementioned method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue described in any one, the mass ratio for the water of pulling an oar and PTA thin-film evaporator blanking residue is preferably 0.2 ~ 0.6:1.
For the aforementioned method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue described in any one, the temperature preferably controlling described raffinate is that in 45 ~ 65 DEG C and described raffinate, acetate concentration is 8 ~ 30wt%.
Beneficial effect of the present invention is:
Have employed special Zeo-karb, selected resin does not adsorb the organism in residue slurry raffinate substantially, even and if when acetate concentration in filtrate is higher, substantially these organism are not adsorbed when dissolved organic matter concentration raises yet, therefore most of resin flow fluid can be returned the making beating stage as making beating water, thus significantly can reduce resin flow fluid extracted amount and the making beating water yield, such acetate concentration is greatly improved, for follow-up acetic acid recovery has laid good basis, not only contribute to the rate of recovery improving acetic acid, also significantly improve the economy of Reclaim Process of Acetic Acid, simultaneously owing to can be used as the previous step of existing multiple acetic acid recovery method, therefore the scope of application of existing multiple acetic acid recovery method can be expanded, promote the perfect further of these methods.
Adopt extraction process recovery of acetic acid from the raffinate of higher acetate concentration, extraction process does not have steam energy consumption, simple to operate and energy-conservation, further increases the economy of recovery rate and recovery process.
Adopt a kind of sodium salt resolve saturated after Zeo-karb, carry out precipitate cobalt manganese with another sodium salt again, achieve and resolve the recycling of agent.With do to resolve compared with agent with strong acid, resolving in the present invention that agent can recycle is another important economy and technical superiority.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
See Fig. 1, the invention provides a kind of method of recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue, object reclaims acetic acid in PTA thin-film evaporator blanking residue and cobalt and manganese, and basic skills is base exchange method Call Provision manganese, extraction process or method of evaporation recovery of acetic acid.The method specifically comprises the steps:
(1) pull an oar: with water to PTA thin-film evaporator blanking residua beating, form residue slurry.Mass ratio for the water of pulling an oar and PTA thin-film evaporator blanking residue is preferably 0.2 ~ 0.6:1.Described thin-film evaporator blanking residue comes from the thin-film evaporator of oxidation mother liquor impurity removing unit in Production of Terephthalic Acid process.The water of making beating can be de-mineralized water or service water.
(2) solid-liquid separation: solid-liquid separation is carried out to described residue slurry, obtains raffinate.The temperature of the described raffinate of preferred control is 45 ~ 65 DEG C.
(3) cationic exchange; With the sodium form Zeo-karb of adsorption of cobalt mn ion carrying out ion-exchange to described raffinate, the cobalt manganese in raffinate is attracted on resin, and the rest part of raffinate flows through resin and obtains resin flow fluid.According to the separation requirement of cobalt and manganese, the sodium form Zeo-karb of preferred employing not adsorb organic compound substantially to cobalt and manganese high adsorption capacity, even and if when acetate concentration in filtrate is higher, these organism wherein are not substantially adsorbed when dissolved organic matter concentration raises yet, therefore most of resin flow fluid can be returned the making beating stage as making beating water, thus significantly can reduce resin flow fluid extracted amount and the making beating water yield, such acetate concentration is greatly improved: in raffinate when not implementing of the present invention after residue slurry filtration, acetate concentration is 1 ~ 5wt%, after implementing this technology, resin flow fluid acetate concentration can be increased to 8 ~ 30wt%, this is the basis that is achieved of the present invention just.So-called " substantially not adsorbing " is determined according to the processing requirement of processing condition and absorption result, adopt existing processing condition to realize and adsorption effect in processing requirement tolerable limit.
(4) Call Provision manganese: the saturated rear parsing agent of Zeo-karb is resolved, obtain desorbed solution, precipitation agent is added to form cobalt manganese precipitation in desorbed solution, filtration obtains coarse filtration cake and filtrate, fully wash coarse filtration cake with washing water again and obtain filter cake and wash filtrate, filter cake is the violent precipitation mixture of cobalt, returns PTA oxidation unit use with acetic acid after can being pulled an oar by filter cake; Filtrate is the aqueous solution of resolving agent containing high density, and this filtrate returned and recycle as Zeo-karb parsing agent, wash filtrate removes waste water.Resolve agent to recycle on stream, only need supplement operating a small amount of parsing agent from the external world and lose, magnitude of recruitment be preferably that resin single resolves parsing agent total amount used 2 ~ 12%.Described washing water are preferably de-mineralized water, the dehydration tower draining of PTA device or PTA refined wastewater, and consumption can be 5 ~ 25 times of washing filter cake quality to be washed, and temperature is preferably 30 ~ 50 DEG C.
(5) resin flow fluid shunting also recovery of acetic acid: the major part of described resin flow fluid is returned described step (1) as circulation fluid and jointly participates in pulling an oar with water; Remaining part carries out process recovery of acetic acid as Extract by operational path A (extraction process) or operational path B (method of evaporation).Preferably make the described resin flow fluid of 60 ~ 95% as described circulation fluid.Preferably make described circulation fluid return step (1) again after cooling, and preferably make described circulation fluid temperature after cooling be down to 20 ~ 40 DEG C.Most of resin flow fluid of the present invention is adopted to return the method for making beating, acetate concentration in described resin flow fluid can be made to bring up to 8 ~ 30wt%, the summation (when adopting operational path A extraction process) making the value of institute's recovery of acetic acid significantly be greater than the summation (when adopting operational path B method of evaporation) of the steam consumption that the steam consumption of subsequent heat evaporation and follow-up PTA dehydration tower increase or the value of recovery of acetic acid to be significantly greater than steam consumption that PTA entrainer recovery tower increases and the steam consumption that follow-up PTA dehydration tower increases, also namely recovery of acetic acid one thing is provided with positive economic benefit, it is the basis that the present invention can produce a desired effect.
Operational path A:
(6) extract: add extraction agent to described Extract and extract.Described extraction agent is preferably the mixture of one or more in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate.Extraction temperature is preferably 40 ~ 60 DEG C, and the mass ratio of extraction agent and Extract is preferably 1.5 ~ 4:1.
(7) decant: carry out decant to extraction liquid, obtains oil phase and aqueous phase, and described oil phase is the extraction agent phase being rich in acetic acid; Containing a small amount of extraction agent in described aqueous phase.
(8) be separated: described oil phase is sent to PTA device dehydration tower to reclaim extraction agent and acetic acid, wherein extraction agent returns described step (6) recycle; Described aqueous phase is sent to PTA device entrainer recovery tower and at the bottom of tower, discharge waste water to reclaim extraction agent simultaneously.
Operational path B:
(9) flash distillation: to the flash distillation again of the first heating evaporation of described Extract, flash distillation gas phase is Acetic Acid-Water steam, and flash distillation liquid phase is waste water.The outlet of preferred control heating evaporation is 100 ~ 120 DEG C, normal pressure, and vaporization rate is 60 ~ 90%, and to control flashing pressure be normal pressure, makes to reach more than 8wt% containing acetic acid in flash distillation gas phase.
(10) dewater: flash distillation gas phase goes PTA device dehydration tower with recovery of acetic acid.
Described parsing agent is preferably the aqueous solution of the mixture of one or more in sodium-chlor, Sodium Bromide, Sodium Fluoride, sodium iodide, SODIUMNITRATE, sodium sulfate, and in this aqueous solution, the mass concentration of solute is preferably 2 ~ 15wt%.Described precipitation agent is preferably the mixture of one or more in sodium sulphite, sodium phosphate, sodium iodate, sodium carbonate, sodium formiate, sodium oxalate.
About the extraction process of the present invention on recovery of acetic acid and these two kinds of route methods of method of evaporation, the advantage of extraction process is that recovery rate is higher, can more than 65% be reached, and relative energy-saving, shortcoming is that in raffinate, the byproduct fraction such as phenylformic acid is extracted into extraction agent phase, and removes PTA dehydration tower mutually with extraction agent and taken back PTA device; The advantage of method of evaporation is that the Acetic Acid-Water steam that evaporation obtains is cleaner, in this steam, benzene carboxylic acid by-products content is little, thus the benzene carboxylic acid by product removing PTA dehydration tower with this steam and take back PTA device is also little, unfortunately recovery rate is lower, about 50%.
Present invention achieves and resolve recycling of agent, the parsing agent of more than 90% can be recycled, and only need supplement a small amount of parsing agent lost in operation, thus substantially increase economy of the present invention.As precipitation agent, recycling of parsing agent is described as parsing agent, sodium carbonate for sodium-chlor below.Cationic exchange resin using state of the present invention is sodium form, Co
2+absorption, parsing, precipitation process chemical equation as follows:
Absorption: Co
2++ 2R-Na → 2Na
++ R
2-Co;
Resolve: NaCl+R
2-Co → CoCl
2+ 2R-Na;
Precipitation: CoCl
2+ Na
2cO
3→ CoCo
3↓ 2NaCl.
From chemical equation above, resolving consumes NaCl, cobalt precipitation process regeneration NaCl, the NaCl consumed and generate is equal in theory, here NaCl is equivalent to intermediary, thus NaCl can recycle in whole parsing-precipitation process, and this process is as the same to manganese.
Acetic acid in the PTA thin-film evaporator blanking residue adopting the present invention to reclaim, can return PTA device and continue to use as solvent; Cobalt manganese precious metal in the PTA thin-film evaporator blanking residue reclaimed, can return PTA device and continue to use as catalyst recirculation.
In order to show method of the present invention at the acetate concentration improving raffinate and the unusual effect improved in recovery rate, applicant discloses two groups of relevant experimental data at this.
Experiment 1:
Adopt traditional method, PTA thin-film evaporator blanking residue 1.1t/h, temperature 190 DEG C, acetic acid content 9.0wt%, pull an oar obtain slurry with 2.2t/h, 15 DEG C of de-mineralized waters, slurry temperature is 45 DEG C, filter slurry and obtain raffinate, analyzing acetic acid content in raffinate is 3.7wt%, and cobalt contents is 0.3%, and Fe content is 0.3%.
Experiment 2:
Adopt method of the present invention, PTA thin-film evaporator blanking residue 1.1t/h, temperature 190 DEG C, acetic acid content 9.0wt%, jointly pull an oar obtain slurry with 0.5t/h, 30 DEG C of de-mineralized waters and 4.5t/h, 30 DEG C of Zeo-karb effluent liquid, slurry temperature is 45 DEG C, Zeo-karb effluent liquid 5.2t/h is obtained after filtering slurry, analyzing acetic acid content in described resin flow fluid is 12.7wt%, be significantly higher than the acetic acid content in the raffinate of experiment 1, for follow-up acetic acid recovery step lays the foundation.Filtrate removes sodium form Zeo-karb, and return to making beating after 4.4t/h resin flow fluid is cooled to 30 DEG C, namely circulation fluid accounts for about 86.6% of resin flow fluid total amount.
Operational path A: get resin flow fluid 0.70kg, by resin flow fluid: the mass ratio of extraction agent=1:3 adds extraction agent n-butyl acetate NBA and extracts in resin flow fluid, extraction temperature is 45 DEG C, obtain oil phase (extraction agent phase) 2.20kg after decant phase-splitting, oil phase is returned dehydration tower and gets final product recovery of acetic acid.In phase-splitting oil phase, acetic acid content is 3.18wt%, and known is as calculated 70.7% to the rate of recovery of acetic acid in PTA thin-film evaporator blanking residue.
Operational path B: get resin flow fluid 0.70kg, heating makes components vaporize, in test gas phase, acetate concentration is entirely solidifying that 0.49kg, acetic acid content are 11.4wt% by it, calculates and knows that to the rate of recovery of acetic acid in PTA thin-film evaporator blanking residue be 56.5%.
The saturated rear 6wt% sodium chloride solution of Zeo-karb resolves to obtain desorbed solution as parsing agent, get desorbed solution 10.0kg, add precipitation agent sodium carbonate to form cobalt manganese precipitation, filter and use 6.0kg de-mineralized water washing leaching cake, obtaining wet cake 400g and filtrate, wet cake is containing cobalt 7.5wt%, containing manganese 7.8wt%, calculating known is 93% to the rate of recovery of cobalt in PTA thin-film evaporator blanking residue, and the rate of recovery of manganese is 92%, filtrate sodium chloride-containing 5.8wt%.Again Zeo-karb is resolved as parsing agent add sodium-chlor to concentration 6wt% in filtrate after, so " sodium-chlor parsing → sodium carbonate precipitation → filtrate is re-used as parsing agent and goes to resolve " recycles sodium-chlor 10 times, actual measurement knows that resin does not have considerable change to the adsorption rate of cobalt manganese with resolving with fresh sodium-chlor compared with agent, and each circulation sodium-chlor average loss rate is that single resolves 4% of sodium-chlor total amount used.
Claims (10)
1. the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue, is characterized in that comprising the steps:
(1) pull an oar: with water to PTA thin-film evaporator blanking residua beating, form residue slurry;
(2) solid-liquid separation: solid-liquid separation is carried out to described residue slurry, obtains raffinate;
(3) cationic exchange: described raffinate is sent to sodium form Zeo-karb, the cobalt manganese in raffinate is attracted on resin, and the rest part of raffinate flows through resin and obtains resin flow fluid;
(4) Call Provision manganese: desorbed solution is resolved to obtain in the saturated rear parsing agent of Zeo-karb, precipitation agent is added to form cobalt manganese precipitation in desorbed solution, filtration obtains coarse filtration cake and filtrate, fully wash coarse filtration cake with washing water again and obtain filter cake and wash filtrate, filter cake is the violent precipitation mixture of cobalt, return PTA oxidation unit after being pulled an oar by filter cake acetic acid to use, filtrate is the aqueous solution of resolving agent containing high density, this filtrate is resolved agent as Zeo-karb recycle, wash filtrate removes waste water;
(5) resin flow fluid shunting also recovery of acetic acid: the major part of described resin flow fluid is returned described step (1) as circulation fluid and jointly participates in pulling an oar with water; Remaining part presses operational path A or operational path B with recovery of acetic acid as Extract;
Operational path A:
(6) extract: add extraction agent to described Extract and extract;
(7) decant: carry out decant to extraction liquid, obtains oil phase and aqueous phase, and described oil phase is the extraction agent phase being rich in acetic acid; Containing a small amount of extraction agent in described aqueous phase;
(8) be separated: described oil phase is sent to PTA device dehydration tower to reclaim extraction agent and acetic acid, wherein extraction agent returns described step (6) recycle; Described aqueous phase is sent to PTA device entrainer recovery tower and at the bottom of tower, discharge waste water to reclaim extraction agent simultaneously;
Operational path B:
(9) flash distillation: to the flash distillation again of the first heating evaporation of described Extract, flash distillation gas phase is Acetic Acid-Water steam, and flash distillation liquid phase is waste water;
(10) dewater: flash distillation gas phase goes PTA device dehydration tower with recovery of acetic acid.
2. the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue as claimed in claim 1, it is characterized in that described parsing agent is the aqueous solution of the mixture of one or more in sodium-chlor, Sodium Bromide, Sodium Fluoride, sodium iodide, SODIUMNITRATE, sodium sulfate, in this aqueous solution, the mass concentration of solute is 2 ~ 15wt%, resolve agent to recycle on stream, extraneous only need supplement operating to lose on a small quantity, magnitude of recruitment is that resin single resolves 2 ~ 12% of parsing agent total amount used; Described precipitation agent is the mixture of one or more in sodium sulphite, sodium phosphate, sodium iodate, sodium carbonate, sodium formiate, sodium oxalate.
3. the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue as claimed in claim 2, it is characterized in that described washing water are de-mineralized water, the dehydration tower draining of PTA device or PTA refined wastewater, consumption is 5 ~ 25 times that wait to wash filter cake quality, and temperature is 30 ~ 50 DEG C.
4. the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue as claimed in claim 2, is characterized in that described extraction agent is the mixture of one or more in methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate.
5. the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue as claimed in claim 4, it is characterized in that extraction temperature is 40 ~ 60 DEG C, the mass ratio of extraction agent and Extract is 1.5 ~ 4:1.
6. the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue as claimed in claim 2, it is characterized in that the outlet controlling heating evaporation is 100 ~ 120 DEG C, normal pressure, vaporization rate is 60 ~ 90%, and control flashing pressure is normal pressure, reaches more than 8wt% in flash distillation gas phase containing acetic acid.
7. as the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue in claim 1-6 as described in any one, it is characterized in that in described step (5), described circulation fluid returns step (1) again after cooling, and described circulation fluid temperature after cooling is down to 20 ~ 40 DEG C.
8., as the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue in claim 1-7 as described in any one, it is characterized in that described circulation fluid accounts for 60 ~ 95% of described resin flow fluid.
9., as the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue in claim 1-8 as described in any one, it is characterized in that the mass ratio 0.2 ~ 0.6:1 of water for pulling an oar and PTA thin-film evaporator blanking residue.
10., as the method for recovery of acetic acid and cobalt manganese from PTA thin-film evaporator blanking residue in claim 1-9 as described in any one, the temperature that it is characterized in that controlling described raffinate is that in 45 ~ 65 DEG C and described raffinate, acetate concentration is 8 ~ 30wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109432874A (en) * | 2018-12-29 | 2019-03-08 | 上海亿鼎电子系统集成有限公司 | A kind of the purification recyclable device and its methods and applications of organic solvent |
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